Compositions including controlled segregated phase domain structure with segregated phase domain array

ABSTRACT

A composition includes a chemical reaction product defining a first surface and a second surface, characterized in that the chemical reaction product includes a segregated phase domain structure including a plurality of domain structures, wherein at least one of the plurality of domain structures includes at least one domain that extends from a first surface of the chemical reaction product to a second surface of the chemical reaction product. The segregated phase domain structure includes a segregated phase domain array. The plurality of domain structures includes i) a copper rich. indium/gallium deficient Cu(In,Ga)Se 2  domain and ii) a copper deficient, indium/gallium rich Cu(In,Ga)Se 2  domain.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of, and claims a benefit of priorityunder 35 U.S.C. 120 from copending utility or design patent applicationU.S. Ser. No. 11/331,422, filed Jan. 12, 2006, the entire contents ofwhich are hereby expressly incorporated herein by reference for allpurposes.

BACKGROUND INFORMATION

1. Field of the Invention

Embodiments of the invention relate generally to the field of materials.More particularly, embodiments of the invention relate to methods ofcontrolling formation of a segregated phase domain structure within achemical reaction product, compositions of matter including such asegregated phase domain structure, and machinery having a complex toolrelief for making such compositions.

2. Discussion of the Related Art

Prior art copper indium selenide based photovoltaics, sometimes calledCIS based PV, are known to those skilled in the art of solar cells.CuInSe is the most reliable and best-performing thin film material forgenerating electricity from sunlight. A concern with this technology isthat raw material supply constraints are going to arise in the future asthe production of CIS PV increases. For instance, indium does not occurnaturally in high concentration ores. Typically, indium is obtained fromthe discarded tailings of zinc ores. As the production of CIS PVapproaches the large scale range of from approximately 10 gigawatts/yearto approximately 100 gigawatts/year, indium supply constraints willbecome manifest. These supply constraints will lead to increased costs.Further, as the production of CIS PV increases, other raw materialsupply constraints will also emerge. What is required is a solution thatreduces the amount of raw materials needed per watt of generatingcapacity in CIS PV thin films.

One approach to reducing the amount of raw materials needed is to reducethe thickness of the CIS PV thin film material. The inherent absorptioncoefficient of CIS is very high (i.e., approximately 10⁵ cm⁻¹). Thismeans that most of the incident light energy can be absorbed with a verythin film of CIS. The use of a back surface reflector can further reducethe thickness necessary to absorb most of the incident light energy.While prior art CIS PV products are typically at least about 2 micronsthick, it is important to appreciate that 0.25 microns is theoreticallysufficient for a CIS PV thin film located on a back surface reflector toabsorb most the incident light energy. What is also required is asolution that produces thinner CIS PV thin films.

Meanwhile, field assisted simultaneous synthesis and transfer technologyhas been developed that is directly applicable to the manufacture ofthinner CIS PV films. Various aspects of this field assistedsimultaneous synthesis and transfer technology (which aspects may or maynot be used together in combination) are described in U.S. Pat. Nos.6,736,986; 6,881,647; 6,787,012; 6,559,372; 6,500,733; 6,797,874;6,720,239; and 6,593,213.

An advantage of field assisted simultaneous synthesis and transfertechnology is that it works better as the precursor stack becomesthinner. For instance, the vapor pressure of selenium in a CIS basedreaction product layer is a function of temperature. The pressure neededto contain the selenium is a function of the temperature required forthe process reaction. It is important to appreciate that the voltage, ifutilized, to achieve a desired pressure goes down as the thickness goesdown. As the required voltage is reduced, the physical demands on thesystem (e.g., stress on the dielectric) go down. Therefore, as theprecursor stack is made thinner, the voltage needed to generate a givenpressure goes down; which reduces stress on the dielectric (for instancea release layer), thereby expanding the scope of materials that can beutilized as a dielectric.

Another advantage of field assisted simultaneous synthesis and transfertechnology is that it enables a lower thermal budget. The lower thermalbudget is a result of higher speed of the field assisted simultaneoussynthesis and transfer technology compared to alternative approachessuch as (physical or chemical) vapor deposition. In addition to the timeand energy savings provided by the field assisted simultaneous synthesisand transfer technology, the quality of the resulting products can alsobe improved. For instance, in the case of manufacturing CIS based PV,the lower thermal budget enabled by the use of field assistedsimultaneous synthesis and transfer technology leads to the reduction ofundesirable reactions, such as between selenium and molybdenum at theinterface between the CIS absorber and the back side metal contact. Thereduction of this undesirable reaction results in reduced tarnishingwhich in-turn results in higher back surface reflectivity.

Recently, it has been demonstrated that CIS thin films made byconventional techniques contain domains resulting from fluctuations inchemical composition^((1-2, 5)). Undesirable recombination of chargecarriers takes place at the boundaries between the nanodomains withinsuch a CIS based PV absorber. Therefore, what is also required is asolution to controlling, and ideally optimizing, the boundaries between,these nanodomains with varying chemical compositions.

Heretofore, the requirements of reduced raw materials requirements,reduced thickness and controlled boundaries between nanodomains referredto above have not been fully met. What is, therefore, needed is asolution that simultaneously solves all of these problems.

SUMMARY OF THE INVENTION

There is a need for the following embodiments of the invention. Ofcourse, the invention is not limited to these embodiments.

According to an embodiment of the invention, a process comprises:providing a first precursor on a first substrate; providing a secondprecursor on a second substrate; contacting the first precursor and thesecond precursor; reacting the first precursor and the second precursorto form a chemical reaction product; and moving the first substrate andthe second substrate relative to one another to separate the chemicalreaction product from at least one member selected from the groupconsisting of the first substrate and the second substrate,characterized in that, to control formation of a segregated phase domainstructure within the chemical reaction product, a constituent of atleast one member selected from the group consisting of the firstprecursor and the second precursor is provided in a quantity thatsubstantially regularly periodically varies from a mean quantity withregard to basal spatial location.

According to another embodiment of the invention, a machine comprises: afirst substrate; and a second substrate coupled to the first substrate,characterized in that, to control formation of a segregated phase domainstructure within a chemical reaction product by controlling an amount ofa constituent of a precursor that is present per unit surface area, atleast one member selected from the group consisting of the firstsubstrate and the second substrate defines a substantially regularlyperiodically varying relief with respect to basal spatial location.

According to another embodiment of the invention, a composition ofmatter comprises: a chemical reaction product defining a first surfaceand a second surface, characterized in that the chemical reactionproduct includes a segregated phase domain structure including aplurality of domain structures, wherein at least one of the plurality ofdomain structures includes at least one domain that extends from a firstsurface of the chemical reaction product to a second surface of thechemical reaction product.

These, and other, embodiments of the invention will be betterappreciated and understood when considered in conjunction with thefollowing description and the accompanying drawings. It should beunderstood, however, that the following description, while indicatingvarious embodiments of the invention and numerous specific detailsthereof, is given by way of illustration and not of limitation. Manysubstitutions, modifications, additions and/or rearrangements may bemade within the scope of an embodiment of the invention withoutdeparting from the spirit thereof, and embodiments of the inventioninclude all such substitutions, modifications, additions and/orrearrangements.

BRIEF DESCRIPTION OF THE DRAWINGS

The drawings accompanying and forming part of this specification areincluded to depict certain embodiments of the invention. A clearerconception of embodiments of the invention, and of the componentscombinable with, and operation of systems provided with, embodiments ofthe invention, will become more readily apparent by referring to theexemplary, and therefore nonlimiting, embodiments illustrated in thedrawings, wherein identical reference numerals (if they occur in morethan one view) designate the same elements. Embodiments of the inventionmay be better understood by reference to one or more of these drawingsin combination with the description presented herein. It should be notedthat the features illustrated in the drawings are not necessarily drawnto scale.

FIGS. 1A-1C are elevational views of pairs of substrates where at leastone of each pair defines a substantially regularly periodically varyingrelief with respect to basal spatial location, representing anembodiment of the invention.

FIGS. 2A-2C are elevational views of pairs of substrates where at leastone of each pair carriers a constituent of a precursor in a quantitythat substantially regularly periodically varies from a mean quantitywith regard to basal spatial location.

FIGS. 3A-3D are plan views of segregated phase domain structuresincluding a segregated phase domain hexagonal array, representing anembodiment of the invention.

FIGS. 3E-3H are plan views of segregated phase domain structuresincluding a segregated phase domain orthogonal array, representing anembodiment of the invention.

FIGS. 4A-4C are schematic elevational views of a process of controllingformation of a segregated phase domain structure using a back surfacecontact that defines a substantially regularly periodically varyingrelief (and electric field strength) with respect to basal spatiallocation, representing an embodiment of the invention.

FIGS. 5A-5C are schematic elevational views of a process of controllingformation of a segregated phase domain structure using a tool thatdefines a substantially regularly periodically varying electric fieldstrength with respect to basal spatial location, representing anembodiment of the invention.

FIGS. 6A-6C are schematic elevational views of a process of controllingformation of a segregated phase domain structure using a tool and a backsurface contact both of which define a substantially regularlyperiodically varying relief with respect to basal spatial location,representing an embodiment of the invention.

FIGS. 6D-6F are schematic elevational views of a process of controllingformation of a segregated phase domain structure using a back surfacecontact which defines a substantially regularly periodically varyingrelief with respect to basal spatial location, representing anembodiment of the invention.

FIGS. 7A-7C are schematic views of a hexagonal domain structure,representing an embodiment of the invention.

FIGS. 8A-8C are schematic elevational views of a process of controllingformation of a segregated phase domain structure using a planar coatingof a first precursor on a surface of a tool where a first precursorconstituent is substantially regularly periodically increased withregard to a basal plane by utilizing a relieved substrate in accordancewith an embodiment of the present invention.

FIGS. 9A-9E are schematic elevational views of a process of controllingformation of a segregated phase domain structure using a first precursoron a surface of a tool where a first precursor constituent issubstantially regularly periodically increased with regard to a basalplane by utilizing a relieved substrate in combination with a liquidcoating containing the first precursor constituent in accordance with anembodiment of the present invention.

FIGS. 10A-10D are schematic elevational views of a process ofcontrolling formation of a segregated phase domain structure using afirst precursor provided on the surface of a tool and a second precursoron a surface of a back contact where a second precursor constituent issubstantially regularly periodically increased by previously depositinga plurality of constituent sources that include an excess of theconstituent relative to a mean quantity in accordance with an embodimentof the present invention.

DESCRIPTION OF PREFERRED EMBODIMENTS

Embodiments of the invention and the various features and advantageousdetails thereof are explained more fully with reference to thenonlimiting embodiments that are illustrated in the accompanyingdrawings and detailed in the following description. Descriptions of wellknown starting materials, processing techniques, components andequipment are omitted so as not to unnecessarily obscure the embodimentsof the invention in detail. It should be understood, however, that thedetailed description and the specific examples, while indicatingpreferred embodiments of the invention, are given by way of illustrationonly and not by way of limitation. Various substitutions, modifications,additions and/or rearrangements within the spirit and/or scope of theunderlying inventive concept will become apparent to those skilled inthe art from this disclosure.

Within this application several publications are referenced by Arabicnumerals, or principal author's name followed by year of publication,within parentheses or brackets. Full citations for these, and other,publications may be found at the end of the specification immediatelypreceding the claims after the section heading References. Thedisclosures of all these publications in their entireties are herebyexpressly incorporated by reference herein for the purpose of indicatingthe background of embodiments of the invention and illustrating thestate of the art.

The instant application contains disclosure that is also contained incopending U.S. Ser. No. 11/331,422 filed Jan. 12, 2006; U.S. Ser. No.11/331,431 filed Jan. 12, 2006 now U.S. Pat. No. 8,084,685; and U.S.Ser. No. 11/330,905 filed Jan. 12, 2006 now U.S. Pat. No. 7,767,904, theentire contents of both of which are hereby expressly incorporated byreference for all purposes. The below-referenced U.S. patents discloseembodiments that are useful for the purposes for which they areintended. The entire contents of U.S. Pat. Nos. 6,736,986; 6,881,647;6,787,012; 6,559,372; 6,500,733; 6,797,874; 6,720,239; 6,593,213; and6,313,479 are hereby expressly incorporated by reference herein for allpurposes.

The context of the invention can include controlling formation of asegregated phase domain structure within a chemical reaction product.The context of the invention can include machinery to control formationof a segregated phase domain structure by controlling an amount of aconstituent of a precursor that is present per unit surface area. Thecontext of the invention can include a chemical reaction product thatincludes a segregated phase domain structure including a plurality ofdomain structures.

The segregated phase domain structure includes a plurality of domainstructures. The invention can include domain structures that definepercolation networks. The invention can include domain structures thatminimize path length required for charge carrier collection (e.g.,columnar domains). At least one of the plurality of domain structurescan include at least one domain that extends from a first surface of thechemical reaction product to a second surface of the chemical reactionproduct. The invention can include domain structures that minimizeboundary surface area (e.g., circular columnar domains) and/or minimizeboundary surface along preferred path directions (e.g., fluted circularcolumnar domains). The invention can include the use of sodium to makeboundaries between domain structures less fuzzy (i.e., more discrete).

The invention can include a characteristic length scale for the(intradomain) size of the domains (e.g., “r” for internal radius). Theinvention can include a characteristic length scale for the(interdomain) size of the separation(s) between domains (e.g., “d” forcenter-to-center distance). By varying the ratio of the characteristicdomain size to characteristic domain separation, the invention enablescontrol of a relative volume of two (or more) domains. By varying theabsolute characteristic values, the invention enables control of theratio of junction volume to the bulk field free volume in two (or more)phase domains. The invention can include controlling the spacing of thedomains to control a ratio of domains and/or phases with regard tovolume or other parameter.

The invention can include a characteristic size distribution of thedomains. Embodiments of the invention can be characterized by a narrowsize distribution of “r” (i.e., monomodal). For instance, embodiments ofthe invention can be characterized by a size distribution in which 80%of the instances of a domain are characterized by a size that is within20% (plus or minus) of a scalar value r. It can be advantageous if 90%of the instances of a domain are characterized by a size that is within10% (plus or minus) of a scalar value “r.” Alternatively, embodiments ofthe invention can be characterized by a plurality of narrow sizedistributions of “r” (i.e., multimodal). Preferred embodiments of theinvention avoid random size distributions (e.g., of “r”).

The invention can include domain structures of a size that are fromapproximately 1 nm to approximately 1 um, preferably from approximately5 nm to approximately 100 nm. The invention can include domainstructures that repeat on multiples of a crystallographic unit celllattice parameter of from approximately 1 nm to approximately 200 nm,preferably from approximately 5 nm to approximately 50 nm. Nevertheless,it is important to appreciate that the exact size (magnitude) of thedomains is not important.

The invention can include a characteristic size distribution of thedomain separations. Embodiments of the invention can be characterized bya narrow size distribution of “d” (i.e., monomodal). For instance,embodiments of the invention can be characterized by a separationdistribution in which 80% of the instances of a domain are characterizedby a separation that is within 20% (plus or minus) of an integermultiple of a scalar value d. It can be advantageous if 90% of theinstances of a domain are characterized by a separation that is within10% (plus or minus) of an integer multiple of a scalar value “d.”Alternatively, embodiments of the invention can be characterized by aplurality of narrow separation distributions of “r” (i.e., multimodal).Preferred embodiments of the invention avoid random separationdistributions (e.g., of “d”).

The invention can include domain structures that repeat (are spaced) ona period of from approximately 1 nm to approximately 1 um, preferablyfrom approximately 5 nm to approximately 100 nm. The invention caninclude domain structures that repeat on multiples of a period of fromapproximately 1 nm to approximately 200 nm, preferably fromapproximately 5 nm to approximately 50 nm. Nevertheless, it is importantto appreciate that the exact size (magnitude) of the domainseparation(s) is not important.

The invention can include domain structures that define 6 fold, 4 foldor other symmetry, in two or three dimensions. However, it is importantto appreciate that the exact symmetry is not important. The inventioncan include domain structures that define short range order. Theinvention can include domain structures that define long range order.

Referring to FIGS. 7A-7C, optimization of a hexagonal domain structurewith regard to minimizing total recombination R will not be described.FIGS. 7A-7B relate to a first order approximation for minimizing totalrecombination R for a hexagonal domain structure array having circularcolumns, assuming the interabsorber junction region is narrow comparedto the scalar dimensions r and d. Referring to FIGS. 7A-7B, a chemicalreaction product 710 defining a first surface 712 and a second surface714 is coupled to a back contact 720. The chemical reaction product 710includes a segregated phase domain structure including a cylindricaldomain structure 701 and a matrix domain structure 702. In this case,the matrix domain structure extends from the first surface 712 of thechemical reaction product 710 to the second surface 714 of the chemicalreaction product 710.

The total volume of each hexagonal cell of height τ₀ is given by((3)^(1/2) d ²τ₀)/2where d is the hexagonal cell-to-cell spacing. The total recombination R(per cell) equals the recombination in cylindrical domain region one R₁plus the recombination in hexagonal matrix domain region two R₂ plus therecombination at the interface of regions one and region two R_(i).R=R ₁ +R ₂ +R _(i)

The recombination in cylindrical domain region one is given byR ₁=ρ₁(volume1)=ρ₁((τ₀−τ₁)πr ²)where ρ_(i) is the bulk recombination rate in cylindrical domain regionone.

The recombination in hexagonal matrix domain region two is given byR ₂=ρ₂(((3)^(1/2) d ²τ₀)/2−(τ₀−τ₁)πr ²)where ρ₂ is the bulk recombination rate in hexagonal matrix domainregion two.

The recombination at the interface between the cylindrical region oneand the matrix domain region two is given byR _(i)=σ_(i)(2πr(τ₀−τ₁)+πr ²)where σ_(i) is the interface (junction) surface recombination velocity.The recombination rates ρ₁ and ρ₂, and the recombination velocity σ_(i)are materials properties that depend on compositions and processinghistories.

FIG. 7C relates to a second order approximation for minimizing totalrecombination R for a hexagonal domain structure array having circularcolumns, where the junction width is not small compared to r and/or d.Referring to FIG. 7C, the total junction width is equal to thecylindrical domain junction width plus the matrix domain junction widthw _(j) =r _(j) +d _(j)

The total recombination R (per cell) equals the recombination in thecylindrical field-free domain region one R₁ plus the recombination inthe hexagonal matrix field-free domain region two R₂ plus therecombination in the annular space charge recombination region oneR_(1j) plus the recombination in the annular space charge recombinationregion two R_(2j).R=R ₁ +R ₂ +R _(1j) +R _(2j)

The following four equations for the terms R₁, R₂, R_(1j) and R_(2j) arevalid when τ₁≧d_(j). If τ₁<d_(j), then set τ₁=0. The recombination incylindrical field-free domain region one is given byR ₁=ρ₁((τ₀−−τ₁ −r _(j))π(r−r _(j))²)where ρ₁ is the bulk recombination rate in cylindrical field-free domainregion one. The recombination in hexagonal matrix field-free domainregion two is given byR ₂=ρ₂(3)^(1/2) d ²τ₀)/2−(τ₀−τ₁ −d _(j))π(r+d _(j))²)where ρ₂ is the bulk recombination rate in hexagonal matrix field-freedomain region two. The recombination in the annular space chargerecombination region one is given byR _(1j)=ρ_(1j)((τ₀−τ₁)πr ²−(τ₀−τ₁ −r _(j))π(r−r _(j))²)where ρ_(1j) is the bulk recombination rate in the annular space chargerecombination region one. The recombination in the annular space chargerecombination region one is given byR _(2j)=ρ_(2j)((τ₀−τ₁ +d _(j))π(r+d _(j))²−(τ₀−τ₁)πr ²)where ρ_(2j) is the bulk recombination rate in the annular space chargerecombination region two. The recombination rates ρ₁, ρ₂, ρ_(1j) andρ_(2j) are materials properties that depend on compositions andprocessing histories.

Referring to FIGS. 1A-1C, the invention can include substantiallyregularly periodically increasing an amount of a precursor by planarcoating a substantially regularly periodically relieved surface.Referring to FIG. 1A, a first substrate 102 includes a substantiallyregularly periodically relieved surface 104. A first precursor 106 iscoupled to the substantially regularly periodically relieved surface104. It can be appreciated that there is relatively more of the firstprecursor 106 corresponding to a basal spatial location centered at arelief cell center position 108 compared to a relief cell edge position110. A second precursor 114 is coupled to a second substrate 112. Thefirst substrate 102 and the second substrate 112 are movable relative toone another. When the first precursor 106 and the second precursor 114are contacted and heated (optionally under the influence of an electricfield) the resulting reaction product can be compositionally rich in theconstituents of the first precursor at a location corresponding to therelief cell center position 108, especially if the basal diffusion rateis much lower than the perpendicular diffusion rate.

Referring to FIG. 1B, a first precursor 126 is coupled to a firstsubstrate 122. A second substrate 132 includes a substantially regularlyperiodically relieved surface 124. A second precursor 134 is coupled tothe substantially regularly periodically relieved surface 124. It can beappreciated that there is relatively more of the second precursor 134 ata relief cell center position 138 compared to a relief cell edgeposition 130. The first substrate 122 and the second substrate 132 aremovable relative to one another. When the first precursor 126 and thesecond precursor 134 are contacted and heated (optionally under theinfluence of an electric field) the resulting reaction product will becompositionally rich in the constituents of the second precursor at alocation corresponding to the relief cell center position 138.

Referring to FIG. 1C, a first substrate 142 includes a substantiallyregularly periodically relieved surface 144. A first precursor 146 iscoupled to the substantially regularly periodically relieved surface144. It can be appreciated that there is relatively more of the firstprecursor 146 at a relief cell center position 158 compared to a reliefcell edge position 150. A second substrate 152 includes a substantiallyregularly periodically relieved surface 145. A second precursor 154 iscoupled to the substantially regularly periodically relieved surface145. It can be appreciated that there is relatively more of the secondprecursor 154 at a relief cell center position 159 compared to a reliefcell edge position 151. The first substrate 142 and the second substrate152 are movable relative to one another. When the first precursor 146and the second precursor 154 are contacted and heated (optionally underthe influence of an electric field) the resulting reaction product willbe compositionally rich in the constituents of the first precursor at alocation corresponding to the relief cell center position 158 and willbe compositionally rich in the constituents of the second precursor at alocation corresponding to the relief cell center position 159.

Referring to FIGS. 2A-2C, the invention can include substantiallyregularly periodically increasing an amount of a precursor by previouslydepositing a plurality of constituent sources that include an excess ofthe constituent relative to a mean quantity. Referring to FIG. 2A, afirst substrate 202 includes a plurality of substantially regularlyperiodically located constituent sources 204. A first precursor 206 iscoupled to the sources 204. It can be appreciated that there isrelatively more of the first precursor 206 in positions 208 without thesources 204 compared to positions 210 with the sources 204. A secondprecursor 214 is coupled to a second substrate 212. The first substrate202 and the second substrate 212 are movable relative to one another.When the first precursor 206 and the second precursor 214 are contactedand heated (optionally under the influence of an electric field) theresulting reaction product will be compositionally rich in theconstituents of the first precursor at locations corresponding to therelief cell center position 208.

Referring to FIG. 2B, a first precursor 226 is coupled to a firstsubstrate 222. A second substrate 232 includes a plurality ofsubstantially regularly periodically located constituent sources 224. Asecond precursor 234 is coupled to the sources 224. It can beappreciated that there is relatively more of the second precursor 234 ata center position 238 compared to edge positions 230. The firstsubstrate 222 and the second substrate 232 are movable relative to oneanother. When the first precursor 226 and the second precursor 234 arecontacted and heated (optionally under the influence of an electricfield) the resulting reaction product will be compositionally rich inthe constituents of the second precursor at a location corresponding tothe relief cell center position 238.

Referring to FIG. 2C, a first substrate 242 includes a plurality ofsubstantially regularly periodically located constituent sources 244. Afirst precursor 246 is coupled to the plurality of substantiallyregularly periodically located sources 244. It can be appreciated thatthere is relatively more of the first precursor 246 at a center position258 compared to an edge position 250. A second substrate 252 includes aplurality of substantially regularly periodically located sources 245. Asecond precursor 254 is coupled to the plurality of substantiallyregularly periodically located sources 245. It can be appreciated thatthere is relatively more of the second precursor 254 at center position259 compared to an edge position 251. The first substrate 242 and thesecond substrate 252 are movable relative to one another. When the firstprecursor 246 and the second precursor 254 are contacted and heated(optionally under the influence of an electric field) the resultingreaction product will be compositionally rich in the constituents of thefirst precursor at a location corresponding to the center position 258and will be compositionally rich in the constituents of the secondprecursor at a location corresponding to the center position 259.

Referring to FIGS. 3A-3H, the relieved surface and/or the constituentsources can be located across a surface to define a hexagonal symmetry,an orthogonal symmetry, or other symmetry and/or space group. Referringto FIG. 3A, the surface relief or sources can define a hexagonal grid310. Referring to FIG. 3B, reaction products 320 whose locationcorrespond to the grid 310 can be columnar (to facilitate charge carriertransport) with a circular circumference. Referring to FIG. 3C, theratio of matrix domain area to columnar domain area can be controlled bylocating the reaction product columns 330 closer to one another (e.g.,so that the columns are just touching). Referring to FIG. 3D, the ratioof matrix domain to columnar domain can lowered still further bylocating the reaction product columns 340 so that they overlap.Referring to FIG. 3E, the surface relief or sources can define anorthogonal grid 350. Referring to FIG. 3F, reaction products 360 whoselocation correspond to the grid 350 can be columnar (to facilitatecharge carrier transport) with a circular circumference. Referring toFIG. 3G, the ratio of matrix domain to columnar domain can be controlledby locating the reaction product columns 370 closer to one another(e.g., so that the columns are just touching). Referring to FIG. 3H, theratio of matrix domain to columnar domain can lowered still further bylocating the reaction product columns 380 so that they overlap.

EXAMPLES

Specific embodiments of the invention will now be further described bythe following, nonlimiting examples which will serve to illustrate insome detail various features. The following examples are included tofacilitate an understanding of ways in which an embodiment of theinvention may be practiced. It should be appreciated that the exampleswhich follow represent embodiments discovered to function well in thepractice of the invention, and thus can be considered to constitutepreferred mode(s) for the practice of the embodiments of the invention.However, it should be appreciated that many changes can be made in theexemplary embodiments which are disclosed while still obtaining like orsimilar result without departing from the spirit and scope of anembodiment of the invention. Accordingly, the examples should not beconstrued as limiting the scope of the invention.

Example 1

Referring to FIGS. 4A-4C, this example relates to an embodiment of theinvention including planar coating of a first precursor 410 on a surfaceof a tool 416 where a first precursor constituent is substantiallyregularly periodically increased by previously depositing a plurality ofconstituent sources 412 that include an excess of the constituentrelative to a mean quantity. This embodiment also includes the use of aswitchable (e.g., on-off), modulatable (e.g., field strength),reversible (e.g., polarity), electric field.

Referring to FIG. 4A, a first precursor 410 includes sources 412. Asecond precursor 420 is provided on a back contact 422. Referring toFIG. 4B, the first precursor 410 and the second precursor 420 arecontacted and heated, and an electric field is applied. With the bias ofthe field applied as depicted in FIG. 4B, the electric field tends todrive at least some of the copper ions away from the tool. The field asdepicted exerts a force on the copper that is opposite the direction ofchemical drive on the copper, and can be termed reverse bias (inappositeto forward bias). Of course, the direction of the field can selected,the magnitude of the field can be controlled and the field can beswitched on and/or off. Meanwhile, the sources 412 form indium-galliumrich beta domains. Referring to FIG. 4C, after the electric field isremoved, the tool is separated and the domains remain intact.

Example 2

Referring to FIGS. 5A-5C, this example relates to an embodiment of theinvention including planar coating of a first precursor on a surface ofa tool where a first precursor constituent is substantially regularlyperiodically increased by previously depositing a plurality ofconstituent sources that include an excess of the constituent relativeto a mean quantity. This embodiment of the invention also includes aback surface contact that is planar coated with a second precursor. Thisembodiment includes the use of a switchable (e.g., on-off), modulatable(e.g., field strength), reversible (e.g., polarity), substantiallyregularly periodically varying electric field strength with respect tobasal spatial location.

Referring to FIG. 5A, a first precursor 510 includes(In/Ga)_(y)(Se)_(1-y) and In/Ga sources 512. The first precursor 510 iscoupled to a planarized release layer 514 that is coupled to asubstantially regularly periodically relieved surface of a tool 516. Thesources 512 can be self assembled at locations corresponding to therelieved surface by photo-ionizing In/Ga particles and applying anegative bias to the tool, or flood gun ionizing the In/Ga particles andapplying a positive bias to the tool. The use of photoionization and/orfloodgun ionization to enable positioning of quantum dots is describedby U.S. Pat. No. 6,313,476. Of course, other methods of self-assemblyand/or deposition can be used to locate the sources 512, such as selforganized epitaxy (e.g., on GaAs) and/or molecular pick-and-placetechniques. A second precursor 520 includes Cu_(x)Se_(1-x). Referring toFIG. 5B, the first precursor 510 and the second precursor 520 arecontacted and heated, and an electric field is applied. The depictedelectric field tends to drive some of the copper ions away from theprojections of the relieved tool, thereby forming copper rich alphadomains. Driving the copper away from the tool helps avoid welding thereaction product to the tool. Meanwhile, the sources 512 formindium-gallium rich beta domains. Referring to FIG. 5C, after theelectric field is removed, the tool is separated and the domains remainintact.

Example 3

Referring to FIGS. 6A-6C, this example relates to an embodiment of theinvention that includes a tool 610 where the quantity of a firstprecursor 612 is substantially regularly periodically increased byplanar coating a substantially regularly periodically relieved surface.This embodiment of the invention also includes a back surface contact614 where a second precursor 616 is substantially planarized.

Referring to FIG. 6A, locations of additional first precursor can beseen. Referring to FIG. 6B, the resulting domains are columnar andextend from a first surface 620 of the reaction product to a secondsurface 622. Referring to FIG. 6C, an emitter 649 is coupled to thereaction product.

Example 4

Referring to FIGS. 6D-6F, this example relates to an embodiment of theinvention that includes a tool 660 that is planar coated with a firstprecursor 662. This embodiment of the invention also includes a backsurface contact 664 where the quantity of a second precursor 668 issubstantially regularly periodically increased by planar coating asubstantially regularly periodically relieved surface.

Referring to FIG. 6D, locations of additional second precursorcorrespond to locations where second precursor rich domains will belocated adjacent the second substrate. Referring to FIG. 6E, only one ofthe resulting domains extends from a first surface 670 of the reactionproduct to a second surface 672. Referring to FIG. 6F, an emitter 699 iscoupled to the reaction product.

Example 5

Referring to FIGS. 8A-8C, this example relates to an embodiment of theinvention including planar coating of a first precursor on a surface ofa tool where a first precursor constituent is substantially regularlyperiodically increased with regard to a basal plane by utilizing arelieved substrate. The result is an excess of the constituent relativeto a mean quantity at locations that correspond to the individualrecesses of the relieved surface of the tool. This embodiment alsoincludes the use of a switchable (e.g., on-off), modulatable (e.g.,field strength), reversible (e.g., polarity), substantially regularlyspatially periodically varying electric field strength with respect tobasal spatial location.

Referring to FIG. 8A, a first precursor 810 is provided on a toolsurface 815. A second precursor 820 is provided on a back contact 822.Referring to FIG. 8B, the first precursor 810 and the second precursor820 are contacted and heated, and an electric field is applied. With thebias of the field applied as depicted in FIG. 8B, the electric fieldtends to drive at least some of the copper ions away from the tool. Itis important to appreciate that the strength of the field is higher atthose locations of the tool surface that are not relieved. Thus, theelectrostatic driving force is also substantially regularly periodicallyincreased with regard to a basal plane. The field as depicted exerts aforce on the copper that is opposite the direction of chemical drive onthe copper, and can be termed reverse bias (inapposite to forward bias).Of course, the direction of the field can selected, the magnitude of thefield can be controlled and the field can be switched on and/or off.Meanwhile, indium-gallium rich beta domains tend to form at locationsthat correspond to the individual recesses of the relieved surface ofthe tool. Referring to FIG. 8C, after the electric field is removed, thetool is separated and the domains remain intact.

Example 6

Referring to FIGS. 9A-9C, this example relates to an embodiment of theinvention including a first precursor on a surface of a tool where afirst precursor constituent is substantially regularly periodicallyincreased with regard to a basal plane by utilizing a relieved substratein combination with a liquid coating containing the first precursorconstituent. The liquid coating is dried and then a remainder of thefirst precursor is deposited. The result is an excess of the constituentrelative to a mean quantity at locations that correspond to theindividual recesses of the relieved surface of the tool. This embodimentagain includes the use of a switchable (e.g., on-off), modulatable(e.g., field strength), reversible (e.g., polarity), substantiallyregularly spatially periodically varying electric field strength withrespect to basal spatial location.

Referring to FIG. 9A, the liquid coating 905 containing the firstprecursor constituent is applied to a tool surface 915. Referring toFIG. 9B, the liquid coating 905 is dried and capillary forces cause thefirst precursor constituent to collect at the deepest portions of theindividual recesses. Referring to FIG. 9C, the remainder 910 of thefirst precursor is planar deposited. A second precursor 920 is providedon a back contact 922. Referring to FIG. 9D, the first precursor 910 andthe second precursor 920 are contacted and heated, and an electric fieldis applied. With the bias of the field applied as depicted in FIG. 9D,the electric field tends to drive at least some of the copper ions awayfrom the relieved substrate. It is important to appreciate that thestrength of the field is higher at those locations of the tool surfacethat are not recessed. In this way, the electrostatic driving force isalso substantially regularly periodically increased with regard to abasal plane. Again, the direction of the field can selected, themagnitude of the field can be controlled and the field can be switchedon and/or off. Referring to FIG. 9E, indium-gallium rich beta domainstend to form at locations that correspond to the individual recesses ofthe relieved surface of the tool. After the electric field is removed,the tool is separated and the domains remain intact.

Example 7

Referring to FIGS. 10A-10D, this example relates to an embodiment of theinvention including a second precursor 1000 on a surface of a backcontact 1020 where a second precursor constituent is substantiallyregularly periodically increased by previously depositing a plurality ofconstituent sources 1010 that include an excess of the constituentrelative to a mean quantity. Again, this embodiment includes the use ofa switchable (e.g., on-off), modulatable (e.g., field strength),reversible (e.g., polarity), electric field.

Referring to FIG. 10A, sources 1010 are formed on the back contact 1020by epitaxy. Referring to FIG. 10B, a first precursor 1030 is provided onthe surface of a tool. The first precursor 1030 and the second precursor1000 are contacted and heated, and the electric field is applied. Withthe bias of the field applied as depicted in FIG. 10C, the electricfield tends to drive at least some of the copper ions away from thesurface of the tool. The field as depicted exerts a force on the copperthat is opposite the direction of chemical drive on the copper, and canbe termed reverse bias. As in the previous examples, the direction ofthe field can selected, the magnitude of the field can be controlled andthe field can be switched on and/or off. Meanwhile, the sources 1010form copper rich alpha domains. Referring to FIG. 10D, after theelectric field is removed, the tool is separated and the domains remainintact.

Practical Applications

A practical application of the invention that has value within thetechnological arts is the manufacture of photovoltaic devices such asabsorber films or electroluminescent phosphors. Further, the inventionis useful in conjunction with the fabrication of semiconductors (such asare used for the purpose of transistors), or in conjunction with thefabrication of superconductors (such as are used for the purpose magnetsor detectors), or the like. There are virtually innumerable uses for anembodiment of the invention, all of which need not be detailed here.

Advantages

Embodiments of the invention can be cost effective and advantageous forat least the following reasons. Embodiments of the invention can improvethe control of formation of a segregated phase domain structure within achemical reaction product. Embodiments of the invention can improve theboundary properties of a plurality of domain structures within thesegregated phase domain structure. Embodiments of the invention canimprove the performance of chemical reaction products that include asegregated phase domain structure. Embodiments of the invention improvequality and/or reduce costs compared to previous approaches.

Definitions

The term layer is generically intended to mean films, coatings andthicker structures. The term coating is subgenerically intended to meanthin films, thick films and thicker structures. The term composition isgenerically intended to mean inorganic and organic substances such as,but not limited to, chemical reaction products and/or physical reactionproducts. The term selenide is intended to mean a material that includesthe element selenium and does not include enough oxygen to precipitate aseparate selenate base; oxygen may be present in selenide. The term toolis intended to mean a substrate intended for re-use or multiple use.

The term program and/or the phrase computer program are intended to meana sequence of instructions designed for execution on a computer system(e.g., a program and/or computer program, may include a subroutine, afunction, a procedure, an object method, an object implementation, anexecutable application, an applet, a servlet, a source code, an objectcode, a shared library/dynamic load library and/or other sequence ofinstructions designed for execution on a computer or computer system).The phrase radio frequency is intended to mean frequencies less than orequal to approximately 300 GHz as well as the infrared spectrum. Groupnumbers corresponding to columns within the periodic table of theelements use the “New Notation” convention as seen in the CRC Handbookof Chemistry and Physics, 81^(st) Edition (2000).

The term substantially is intended to mean largely but not necessarilywholly that which is specified. The term approximately is intended tomean at least close to a given value (e.g., within 10% of). The termgenerally is intended to mean at least approaching a given state. Theterm coupled is intended to mean connected, although not necessarilydirectly, and not necessarily mechanically. The term proximate, as usedherein, is intended to mean close, near adjacent and/or coincident; andincludes spatial situations where specified functions and/or results (ifany) can be carried out and/or achieved. The term deploying is intendedto mean designing, building, shipping, installing and/or operating.

The terms first or one, and the phrases at least a first or at leastone, are intended to mean the singular or the plural unless it is clearfrom the intrinsic text of this document that it is meant otherwise. Theterms second or another, and the phrases at least a second or at leastanother, are intended to mean the singular or the plural unless it isclear from the intrinsic text of this document that it is meantotherwise. Unless expressly stated to the contrary in the intrinsic textof this document, the term or is intended to mean an inclusive or andnot an exclusive or. Specifically, a condition A or B is satisfied byany one of the following: A is true (or present) and B is false (or notpresent), A is false (or not present) and B is true (or present), andboth A and B are true (or present). The terms a or an are employed forgrammatical style and merely for convenience.

The term plurality is intended to mean two or more than two. The termany is intended to mean all applicable members of a set or at least asubset of all applicable members of the set. The phrase any integerderivable therein is intended to mean an integer between thecorresponding numbers recited in the specification. The phrase any rangederivable therein is intended to mean any range within suchcorresponding numbers. The term means, when followed by the term “for”is intended to mean hardware, firmware and/or software for achieving aresult. The term step, when followed by the term “for” is intended tomean a (sub)method, (sub)process and/or (sub)routine for achieving therecited result.

The terms “comprises,” “comprising,” “includes,” “including,” “has,”“having” or any other variation thereof, are intended to cover anon-exclusive inclusion. For example, a process, method, article, orapparatus that comprises a list of elements is not necessarily limitedto only those elements but may include other elements not expresslylisted or inherent to such process, method, article, or apparatus. Theterms “consisting” (consists, consisted) and/or “composing” (composes,composed) are intended to mean closed language that does not leave therecited method, apparatus or composition to the inclusion of procedures,structure(s) and/or ingredient(s) other than those recited except forancillaries, adjuncts and/or impurities ordinarily associated therewith.The recital of the term “essentially” along with the term “consisting”(consists, consisted) and/or “composing” (composes, composed), isintended to mean modified close language that leaves the recited method,apparatus and/or composition open only for the inclusion of unspecifiedprocedure(s), structure(s) and/or ingredient(s) which do not materiallyaffect the basic novel characteristics of the recited method, apparatusand/or composition.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. In case of conflict, thepresent specification, including definitions, will control.

Conclusion

The described embodiments and examples are illustrative only and notintended to be limiting. Although embodiments of the invention can beimplemented separately, embodiments of the invention may be integratedinto the system(s) with which they are associated. All the embodimentsof the invention disclosed herein can be made and used without undueexperimentation in light of the disclosure. Although the best mode ofthe invention contemplated by the inventor(s) is disclosed, embodimentsof the invention are not limited thereto. Embodiments of the inventionare not limited by theoretical statements (if any) recited herein.

The individual steps of embodiments of the invention need not beperformed in the disclosed manner, or combined in the disclosedsequences, but may be performed in any and all manner and/or combined inany and all sequences. The individual components of embodiments of theinvention need not be formed in the disclosed shapes, or combined in thedisclosed configurations, but could be provided in any and all shapes,and/or combined in any and all configurations. The individual componentsneed not be fabricated from the disclosed materials, but could befabricated from any and all suitable materials. Homologous replacementsmay be substituted for the substances described herein.

It can be appreciated by those of ordinary skill in the art to whichembodiments of the invention pertain that various substitutions,modifications, additions and/or rearrangements of the features ofembodiments of the invention may be made without deviating from thespirit and/or scope of the underlying inventive concept. All thedisclosed elements and features of each disclosed embodiment can becombined with, or substituted for, the disclosed elements and featuresof every other disclosed embodiment except where such elements orfeatures are mutually exclusive. The spirit and/or scope of theunderlying inventive concept as defined by the appended claims and theirequivalents cover all such substitutions, modifications, additionsand/or rearrangements.

The appended claims are not to be interpreted as includingmeans-plus-function limitations, unless such a limitation is explicitlyrecited in a given claim using the phrase(s) “means for” and/or “stepfor.” Subgeneric embodiments of the invention are delineated by theappended independent claims and their equivalents. Specific embodimentsof the invention are differentiated by the appended dependent claims andtheir equivalents.

REFERENCES

(1) B. J. Stanbery, “The intra-absorber junction (IAJ) model for thedevice physics of copper indium selenide-based photovoltaics,”0-7803-8707-4/05 IEEE, presented Jan. 5, 2005, pages 355-358.

(2) Y. Yan, R. Noufi, K. M. Jones, K. Ramanathan, M. M. Al-Jassim and B.J. Stanbery, “Chemical fluctuation-induced nanodomains in Cu(In,Ga)Se₂films,” Applied Physics Letters 87, 121904 American Institute ofPhysics, Sep. 12, 2005.

(3) Billy J. Stanbery, “Copper indium selenides and related materialsfor photovoltaic devices,” 1040-8436/02 CRC Press, Inc., 2002, pages73-117.

(4) B. J. Stanbery, S. Kincal, L. Kim, T. J. Anderson, O. D. Crisalle,S. P. Ahrenkiel and G. Lippold “Role of Sodium in the Control of DefectStructures in CIS,” 0-7803-5772-8/00 IEEE, 2000, pages 440-445.

(5) 20th European Photovoltaic Solar Energy Conference, 6-10 Jun. 2005,Barcelona, Spain, pages 1744-1747.

What is claimed is:
 1. A composition, comprising a chemical reactionproduct defining a first surface and a second surface, wherein thechemical reaction product includes a segregated phase domain structureincluding a plurality of domain structures, wherein at least one of theplurality of domain structures includes at least one domain that extendsfrom the first surface of the chemical reaction product to the secondsurface of the chemical reaction product, wherein the segregated phasedomain structure includes a segregated phase domain array and whereinthe plurality of domain structures includes i) a copper rich,indium/gallium deficient Cu(In,Ga)Se₂ domain and ii) a copper deficient,indium/gallium rich Cu(In,Ga)Se₂ domain.
 2. The composition of claim 1,wherein the plurality of domain structures includes two domains thatextend from the first surface of the chemical reaction product to thesecond surface of the chemical reaction product.
 3. The composition ofclaim 1, wherein the plurality of domain structures includes i) a firstdomain that extends from the first surface of the chemical reactionproduct to the second surface of the chemical reaction product and ii) asecond domain that does not extend from the first surface of thechemical reaction product to the second surface of the chemical reactionproduct.
 4. The composition of claim 1, wherein the chemical reactionproduct includes a semiconductor absorber.
 5. The composition of claim1, wherein the segregated phase domain array includes a hexagonal arraythat defines an intradomain size r and an interdomain spacing d.
 6. Thecomposition of claim 5, wherein the composition includes a semiconductorand the ratio of r/d and the magnitudes of the intradomain size r andthe interdomain spacing d are controlled to substantially minimize atotal recombination R characteristic of the semiconductor.
 7. Thecomposition of claim 1, wherein the plurality of domain structures arecrystallographically coherent.
 8. The composition of claim 1, whereinthe chemical reaction product includes one member selected from thegroup consisting of a layer, a coating and a film.
 9. A photovoltaicdevice comprising the composition of claim
 1. 10. A composition,comprising a chemical reaction product defining a first surface and asecond surface, wherein the chemical reaction product includes asegregated phase domain structure including a plurality of domainstructures, wherein at least one of the plurality of domain structuresincludes at least one domain that extends from the first surface of thechemical reaction product to the second surface of the chemical reactionproduct, wherein the plurality of domain structures includes two domainsthat extend from the first surface of the chemical reaction product tothe second surface of the chemical reaction product, wherein thesegregated phase domain structure includes a segregated phase domainarray including a hexagonal array that defines an intradomain size r andan interdomain spacing d and wherein the plurality of domain structuresincludes i) a copper rich, indium/gallium deficient Cu(In,Ga)Se₂ domainand ii) a copper deficient, indium/gallium rich Cu(In,Ga)Se₂ domain. 11.The composition of claim 10, wherein the composition includes asemiconductor and the ratio of r/d and the magnitudes of the intradomainsize r and the interdomain spacing d are controlled to substantiallyminimize a total recombination R characteristic of the semiconductor.12. The composition of claim 10, wherein the plurality of domainstructures are crystallographically coherent.
 13. The composition ofclaim 10, wherein the chemical reaction product includes one memberselected from the group consisting of a layer, a coating and a film. 14.A photovoltaic device comprising the composition of claim
 10. 15. Acomposition, comprising a chemical reaction product defining a firstsurface and a second surface, wherein the chemical reaction productincludes a segregated phase domain structure including a plurality ofdomain structures, wherein at least one of the plurality of domainstructures includes at least one domain that extends from the firstsurface of the chemical reaction product to the second surface of thechemical reaction product, wherein the plurality of domain structuresincludes i) a first domain that extends from the first surface of thechemical reaction product to the second surface of the chemical reactionproduct and ii) a second domain that does not extend from the firstsurface of the chemical reaction product to the second surface of thechemical reaction product, wherein the segregated phase domain structureincludes a segregated phase domain array, wherein the segregated phasedomain array includes a hexagonal array that defines an intradomain sizer and an interdomain spacing d and wherein the plurality of domainstructures includes i) a copper rich, indium/gallium deficientCu(In,Ga)Se₂ domain and ii) a copper deficient, indium/gallium richCu(In,Ga)Se₂ domain.
 16. The composition of claim 15, wherein thecomposition includes a semiconductor and the ratio of r/d and themagnitudes of the intradomain size r and the interdomain spacing d arecontrolled to substantially minimize a total recombination Rcharacteristic of the semiconductor.
 17. The composition of claim 15,wherein the plurality of domain structures are crystallographicallycoherent.
 18. The composition of claim 15, wherein the chemical reactionproduct includes one member selected from the group consisting of alayer, a coating and a film.
 19. A photovoltaic device comprising thecomposition of claim 15.